Process for producing 1-acetoxy-3-(substituted phenyl)propene compound

ABSTRACT

The compounds represented by the formula (I) are produced by reacting benzene compound of the formula (IV) or (V) with alkenylidene diacetate of the formula (VI) in the presence of a catalyst comprising one or more members selected from (a) halogenated boron compounds,
     (b) triflate compounds of Group 11 elements,   (c) halogenated compounds of Group 12 elements, and   (d) triflate and halogenated compounds of tin and atomic numbers 58 and 66 to 71 elements.   

     
       
         
         
             
             
         
       
         
         
           
             R 1 , R 2 =H or C1–C10 alkyl group 
             A=Substituted phenyl group corresponding to a compound of formula (IV) or (V), 
             R 3 , R 4 =H or C1–C4 alkyl group, m=0 or 1–4, n=1 to 5, k=1 or 2.

TECHNICAL FIELD

The present invention relates to a process for producing a1-acetoxy-3-(substituted phenyl)propene compound. More particularly, thepresent invention relates to a process for producing a1-acetoxy-3-(substituted phenyl)propene compound having a phenyl groupsubstituted with a substituent group, for example, an alkoxy group or analkylenedioxy group, and located in the 3-position of the propenecompound.

The 1-acetoxy-3-(substituted phenyl)propene compound produced by theprocess of the present invention is useful as an intermediate materialfor perfumes, pharmaceuticals, agricultural chemicals and other organicsynthetic chemicals.

BACKGROUND ART

Bull, Soc, Chim, Frame, 1961, p1195–1198, discloses, as a process forsynthesizing a 1-acetoxy-3-(substituted phenyl)propene compound, aprocess for synthesizing 1-acetoxy-3-(3,4-dimethoxyphenyl)propene byreacting 1,2-dimethoxybenzene with an alkenylidene diacetate in thepresence of titanium tetrachloride activated with a borontrifluoride-ether complex. This literature reported that the yield ofthe target compound produced by this process was 62%, which wasunsatisfactory. The inventors of the present invention tried to tracethe process of the above-mentioned literature, and as a result, foundthat the yield of the target compound was only 12%, a plurality ofby-products were produced, and the resultant product mixture liquidexhibited a brown color (refer to Comparative Example 3 of the presentapplication). Also, it was confirmed that titanium tetrachloride, usedfor the process of the literature, was a chemically unstable compound tosuch an extent that this compound is decomposed by moisture in theatmospheric air, and thus complicated and meticulous care is needed inhandling this compound.

Further, the inventors of the present invention tried to apply theprocess of the literature to the reaction of 3,4-methylenedioxy benzenewith an alkenylidene diacetate and found that the titanium tetrachlorideactivated by boron trifluoride-ether complex caused a decompositionreaction of 3,4-methylenedioxybenzene to be promoted, and the yield ofthe target compound was 43% and unsatisfactory (refer to ComparativeExample 1 of the present application). Furthermore, the inventors of thepresent invention tried to effect the reaction by using titaniumtetrachloride in an amount of 0.1 mole per mole of alkenylidenediacetate, to control or prevent the decomposition of3,4-methylenedioxybenzene. As a result, the yield of the target compounddecreased to 9.8% (refer to Comparative Example 2 of the presentapplication).

Japanese Unexamined Patent Publication No. 55–141437 discloses a processfor producing 1-acetoxy-2-methyl-3-(4-t-butylphenyl)propene by reactingt-butylbenzene with methacrolein and acetyl chloride in the presence ofa stoichiometric amount of a Lewis acid. In this process, when titaniumtetrachloride was used as Lewis acid, the yield of the target compoundwas 46.2%, and when boron trifluoride-ether complex was employed as aLewis acid, the yield of the target compound was 2.3%. In each of theabove-mentioned cases, the target compound yield was low andunsatisfactory.

SUMMARY

We provide a process for producing a 1-acetoxy-3-(substitutedphenyl)propene compound useful, as an intermediate material, forperfumes, pharmaceuticals, agricultural chemicals and other organicsynthetic chemicals with high efficiency and an easy process.

The process for producing a 1-acetoxy-3-(substituted phenyl)propenecompound represented by the general formula (I):

in which formula (I), R¹ and R², respectively and independently fromeach other, represent a member selected from the groups consisting of ahydrogen atom and alkyl groups having 1 to 10 carbon atoms, R¹ and R²may form, together with carbon atoms located in the 2- and 3-positionsof the propene group, a cyclic group; and A represents a member selectedfrom a group of substituted phenyl groups represented by the formulae(II) and (III):

wherein R³ and R⁴, respectively and independently from each other,represent an alkyl group having 1 to 4 carbon atoms, m represents aninteger of 0 or 1 to 4, n represents an integer of 1 or 5 and krepresents an integer of 1 or 2,

comprises reacting a benzene compound selected from those represented bythe general formulae (IV) and (V):

in which formula (IV) and (V), R³ and R⁴ and n, m and k are as definedabove, with an alkenylidene diacetate compound represented by thegeneral formula (VI):

in which formula (VI), R¹ and R² are as defined above,

in the presence of a catalyst comprising at least one compound selectedfrom the group consisting of (a) halogenated boron compounds, (b)triflate compounds of Group 11 elements of the Periodic Table, (c)halogenated compounds of Group 12 elements of the Periodic Table, and(d) triflate compounds and halogenated compounds of tin and lanthanoidelements of atomic numbers 58 and 66 to 71.

The benzene compounds represented by the formula (IV) are preferablyselected from the group consisting of anisole, veratrol, hydroquinonedimethylether, Pyrogallol tri-methylether and hydroxyhydroquinonetrimethylether.

The benzene compounds represented by the formula (V) are preferablyselected from the group consisting of 1,2-methylenedioxybenzene and1,2-ethylenedioxybenzene.

The alkenylidene diacetate is preferably selected from the groupconsisting of 3,3-diacetoxy-2-methylepropene,3,3-diacetoxy propene, 3,3-diacetoxy- 1-methyipropene,3,3-dia-cetoxy-2-ethylpropene,3,3-diacetoxy-1-ethyipropene, and3,3-diacetoxy-1-ethyl-2-methyl-propene.

The reaction is preferably carried out in a molar ratio of the benzenecompound to the alkenylidene diacetate compound of 1:1 to 50:1.

The catalyst is preferably present in an amount of 0.005 to 1 mole permole of the alkenylidene diacetate compound.

The halogenated boron compounds (a) usable for the catalyst arepreferably selected from boron fluorides, boron trifluoride-diethylethercomplexes, borontrifluoride-tetra-hydrofuran complexes, borontrifluoride-acetic acid complex salt, boron trifluoride dehydrate, andboron trifluoride-n-butylether complexes.

The triflate compounds (b) of Group II elements of the Periodic Tableusable for the catalyst are preferably selected from the groupconsisting of copper triflate and silver triflate.

The halogenated compounds (c) of Group 12 elements of the Periodic Tableusable for the catalyst are preferably selected from the groupconsisting of zinc fluoride, zinc chloride, zinc bromide, zinc iodide,cadmium fluoride, cadmium chloride, cadmium bromide, cadmium iodide,hydrogen fluoride, mercury chloride, mercury bromide, and mercuryiodide.

The triflate and halogenated compounds (d) of tin and lanthanoidelements of atomic numbers 58 and 66 to 71 are preferably selected fromthe group consisting of triflates, fluorides, chloride, bromides, andiodide of tin, cerium, dysprosium, holmium, erbium, thulium, ytterbiumand lutetium.

The reaction is preferably carried out in an atmosphere consisting of anon-reactive gas to the above-mentioned compounds of the formulae (IV),(V) and (VI), the above-mentioned catalyst and the resultant reactionproducts.

The compounds of the formula (I) are preferably selected from thecompounds represented by the general formula (VII):

in which formula (VII), R¹, R² are as defined above, B represents amember selected from a group of substituted phenyl groups represented bythe formulae (VIII) and (IX):

in which formulae (VIII) and (IX), R³ and R⁴ and k are as defined above.

The compounds represented by the formula (VII) are new compounds.

The compound of the formula (I) is preferably selected from1-acetoxy-3-(3,4-C1 to C2 alkylene dioxyphenyl)propenes represented bythe formulae (X) and (XI):

The compounds represented by the formulae (X) and (XI) are newcompounds.

Preferably in the formulae (X) and (XI), R¹ represents a hydrogen atomand R² represents a methyl group.

The compound of the formula (I) is preferably selected from the groupsconsisting of 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene,1-acetoxy-2-methyl-3-(3,4ethylenedioxyphenyl)propene,1-acetoxy-2-methyl-3-(4-methoxyphenyl) propene,1-acetoxy-yl-3-(2,5-dimethoxyphenyl)) propene, 1-acetoxy-2-methyl-3-(3,4-dimethoxyphenyl)propene.

Among the compounds, 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene, 1-acetoxy-2-methyl-3-(3,4-ethylenedioxyphenyl)propene, and1-acetoxy-2-methyl-3-(2,5-dimethoxyphenyl)propene are new compounds.

The Periodic Table is based on the 18 Groups-Type Elemental PeriodicTable, IUPAC and Nomenclature in Inorganic Chemistry, 1990 Rule.

Also, the term “triflate” refers to trifluoromethanesulfonate.

DETAILED DESCRIPTION

The 1-acetoxy-3-(substituted phenyl)propene compound produced by theprocess is represented by the above-mentioned general formula (I) andincludes a plurality of types of stereoisomers due to asymmetric carbonatoms and/or a double bond contained in the molecule of the compound.

The process for producing 1 -acetoxy-3-(substituted phenyl)propenecompound comprises the step of reacting at least one member selectedfrom a group of benzene compounds represented by the above-mentionedgeneral formulae (IV) and (V) with an alkenylidene diacetate representedby the general formula (VI) in the presence of a specific catalyst whichwill be illustrated in detail hereinafter. The benzene compoundsrepresented by the formulae (IV) and (V) correspond to the substitutedphenyl groups represented by the general formula (II) and (III), and thealkenylidene diacetate of the general formula (VI) corresponds to a1-acetoxypropene group bonded to the A group contained in the generalformula (I).

The specific catalysts for the process comprises at least one memberselected from the group consisting of:

-   -   (a) halogenated boron compounds,    -   (b) triflate compounds of Group II elements of the Periodic        Table,    -   (c) halogenated compounds of Group 12 elements of the Periodic        Table, and (d) triflate compounds and halogenated compounds of        tin and lanthanoid elements of atomic numbers 58 and 66 to 71.

In the process, the benzene compound represented by the general formula(IV) is preferably selected from anisole, veratrole,hydroquinonedimethylether, pyrogalloltrimethylether, and hydroxylhydroquinonetrimethylether. Among them, anisol and veratrol areparticularly preferably used. These compounds may be of a common tradegrade.

Also, the benzene compound represented by the general formula (V) ispreferably selected from 1,2-methylenedioxybenzene and1,2-ethylenedioxybenzene.

Further, the alkenylidene diacetate represented by the general formula(VI) is preferably selected from the group consisting of3,3-diacetoxy-2-methylpropene, 3,3-diacetoxy-propene,3,3-diacetoxy-l-methylpropene, 3,3-diacetoxy-2-ethylpropene,3,3-diacetoxy-1-ethylpropene and 3,3-diacetoxy-1-ethyl-2-methylpropene.These compounds may be in trade grade and, optionally may be preparedwith an α,β-unsaturated aldehyde and acetic anhydride in accordance withthe process disclosed in Bull, Soc, Chim, Frame, 1961, p1194 to 1198.These compounds include isomers.

In the alkenylidene diacetate represented by the general formula (VI),groups R¹ and R² may be bonded to each other to form, together with thecarbon atoms in the 2- and 3-positions of the propene group, a cyclicgroup.

The cyclic group is preferably a cyclopentane or cyclohexane group, morepreferably a cyclohexane group.

The α,β-unsaturated aldehyde usable for the preparation of thealkenylidene diacetate preferably include acrolein, methacrolein,crotonaldehyde, α,β-dimethylacrolein, α-ethylacrolein, β-ethylacrolein,β-propylacrolein and α-cyclohexylacrolein, more preferably acrolein,methacrolein and crotonaldehyde, still more preferably methacrolein.

The halogenated boron compound (a) for the catalyst usable for theprocess includes, for example, boron fluoride, borontrifluoride-diethylether complex, boron trifluoride-tetrahydrofurancomplex, boron trifluoride-acetic acid complex salt, borontrifluoride-dihydrate and boron trifluoride-n-butylether complex. Amongthem, boron trifluoride-ether complex and boron trifluoride-acetic acidcomplex salt are more preferably employed. These compounds may be of atrade grade.

The triflate compound of the Group 11 elements for the catalyst ispreferably selected from copper triflate and silver triflate.

The halogenated compounds (c) of the Group 12 elements for the catalystpreferably include zinc fluoride, zinc chloride, zinc bromide, zinciodide, cadmium fluoride, cadmium chloride, cadmium bromide, cadmiumiodide, mercury fluoride, mercury chloride mercury bromide and mercuryiodide. Among them, the halogenated compounds of zinc are morepreferably employed, and zinc chloride is still more preferablyemployed.

The triflate compounds and halogenated compounds (d) of tin and atomicnumber 58 and 66 to 71 lanthanoid elements preferably include tintriflate, tin fluoride, tin chloride, tin bromide, tin iodide, ceriumfluoride, cerium chloride, cerium bromide, cerium iodide, ceriumtriflate, dysprosium fluoride, dysprosium chloride, dysprosium bromide,dysprosium iodide, dysprosium triflate, holmium fluoride, holmiumchloride, holmium bromide, holmium iodide, holmium triflate, erbiumfluoride, erbium chloride, erbium bromide, erbium iodide, erbiumtriflate, thulium fluoride, thulium chloride, thulium bromide, thuliumiodide, thulium triflate, ytterbium fluoride, ytterbium chloride,ytterbium bromide, ytterbium iodide, ytterbium triflate, lutetiumfluoride, lutetium chloride, lutetium bromide, lutetium iodide, lutetiumtriflate, and hydrates of the above-mentioned compounds. Among them, tinchloride, tin triflate, erbium triflate, thulium triflate, ytterbiumchloride, ytterbium triflate and lutetium triflate are more preferablyemployed. Still more preferably, tin chloride and ytterbium chloride areemployed.

In the process, the catalyst is preferably employed in an amount of0.005 to 1 mole preferalby 0.01 to 0.5 mole, still more preferably 0.01to 0.2 mole, per mole of the alkenylidene diacetate. If the catalyst isused in an amount of more than 1 mole, complicated procedures may beneeded for recovery, decomposition and disposal of the catalyst afterthe reaction is completed, and may cause the practice of the process inthe industrial scale to be inconvenient. Also, if the amount of thecatalyst is less than 0.005 mole, the reaction may not be completedwithin a practical time, for example, within 24 hours.

The reaction in the may be carried out in a solvent medium. Usually, thereaction is preferably not carried out in a solvent medium. For thesolvent, aromatic hydrocarbons, for example, benzene and toluene,xylene; halogenated aromatic hydrocarbons, for example, chlorobenzene;and halogenated aliphatic hydrocarbons, for example, methylene chlorideand dichloroethane, may be employed.

The reaction temperature for the process can be appropriatelyestablished in response to the types and concentrations of the startingcompounds and catalysts. Usually, the reaction is carried out at atemperature of −10 to 80° C., more preferably 0 to 60° C. The reactiontime for the process can be appropriately established in considerationof the types and concentrations of the starting compounds and catalystsand the reaction temperature. Usually, the reaction time is preferablyin the range of from 0.5 to 24 hours, more preferably 0.5 to 12 hours.

There is no specific limitation to the type of the reaction atmospherefor the process. Usually, the reaction of the process is carried out ina gas nonreactive to the starting compounds (namely, the compounds ofthe general formulae (I) and (II), the catalyst and the resultantproducts, for example, a gas atmosphere or flow comprising at least onegas selected from nitrogen gas and inert gases, for example, argon gas.The reaction is usually carried out at the ambient atmospheric pressure.However, the reaction pressure is not limited to that mentioned above.

The 1-acetoxy-3-(substituted phenyl)propene compound produced inaccordance with the process is usually refined by separating thecompound from the resultant reaction mixture liquid after the reactionis completed by a usual separate-recovery procedure, for example, anextraction, a concentration and a filtration and then optionally byapplying a refining procedure, for example, a distillation,recrystallization and various chromatographies, to theseparate-recovered fraction.

In the general formula (I) representing the 1-acetoxy-3-(substitutedphenyl)propene compound produced by the process, R¹ and R² represent ahydrogen atom or a C1–C10 alkyl group, and preferably, at least one ofR¹ and R² represents a C1–C10 alkyl group. The C1–C10 alkyl groupsrepresented by R¹ and R² include methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, nonyl and decyl groups. These groups respectivelyinclude a plurality of isomers. The alkyl group represented by R¹ and R²is preferably a methyl group.

In the general formula (I), the alkyl groups represented by R¹ and R²may be bonded (or fused) at the terminals thereof to each other to form,together with the carbon atoms located in the 1- and 2-positions of thepropene group, a cyclic group. The cyclic group is preferably, forexample, a cyclopentane or cyclohexane group, more preferably acyclohexane group.

In the compound of the general formula (I), R³ and R⁴ in the substitutedphenyl group (A) represented by the general formulae (II) and (III),respectively and independently from each other represent a C1–C4 alkylgroup, m represents an integer of 0 (zero) or 1 to 4, n represents aninteger of 1 to 5, k represents an integer of 1 or 2. The C1–C4 alkylgroups represented by R³ and R⁴ include methyl, ethyl, propyl and butylgroups, and each alkyl group includes a plurality of isomers. The C1–C4alkyl groups preferably selected from methyl, ethyl, n-propyl isopropyl,n-butyl, isobutyl and sec-butyl

Among the compounds of the general formula (I) produced by the process,the 1-acetoxy-3-(substituted phenyl)propene compounds represented by thegeneral formula (VII):

in which formula (VII), R¹, R² are as defined above, B represents amember selected from a group of substituted phenyl groups represented bythe formulae (VIII) and (IX):

in which formulae (VIII) and (IX), R³ and R⁴ and k are as defined above,are novel compounds.

In the case where the A in the general formula (I) represents thesubstituted phenyl groups of the general formula (III), the1-acetoxy-3-(substituted phenyl)propene compounds represented by thegeneral formula (I) is preferably selected from the 1 -acetoxy-3-(3,4-C1–C2alkylenedioxy-phenyl)propenes represented by the generalformulae (X) and (XI). In this case, in the general formulae (X) and(XI), preferably, R¹ represents a hydrogen atom and R² represents amethyl group.

Also, in the general formula (I) representing the1-acetoxy-3-(substituted phenyl)propene compounds, in the case where Arepresents the substituted phenyl groups represented by the generalformula (II), the substituted phenyl group (II) preferably selected from4-methoxyphenyl group, 2,5-dimethoxyphenyl group and 3,4-dimethoxyphenylgroup.

Accordingly, the 1-acetoxy-3-(substituted phenyl)propene compoundsrepresented by the general formula (I) are preferably selected from thegroup consisting of 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene,1-acetoxy-2-methyl-3-(3,4-ethylene-dioxyphenyl) propene,1-acetoxy-2-methyl-3-(4-methoxyphenyl)propene,1-acetoxy-2-methyl-3-(2,5-dimethoxyphenyl)propene, and1-acetoxy-2-methyl-3-(3,4-dimethoxyphenyl)propene.

EXAMPLES

Selected aspects of the invention will be further illustrated by thefollowing examples which are not intended to limit the scope of theappended claims in any way.

In the examples, the yield of 1-acetoxy-2-methyl-3-(substitutedphenyl)propene was calculated on the basis of mass of3,3-diacetoxy-2-methylpropene employed.

Example 1

In an argon gas atmosphere at a temperature of 20° C., a 20 ml flask wascharged with a mixed solution of 6.83 g (56.0 m moles) of1,2-methylenedioxybenzene and a solution 1.05 g (5.6 m moles) of3,3-diacetoxy-2-methylpropene in a purity degree of 91.8% by mass, andthe mixed solution was mixed with 74 mg (0.52 m mole) of borontrifluoride-diethylether complex. The resultant mixture was stirred at atemperature of 23° C. for one hour to provide a reaction liquid. Thereaction liquid was mixed with 50 ml of ethyl acetate, and a resultantorganic phase layer formed in the reaction liquid is separated andcollected, washed three times with water in an amount of 50 ml, anddried with anhydrous sodium sulfate to remove the solvent. The resultantresidue was refined by a column chromatography on silica gel using asolvent ethyl acetate/n-hexane mixture in a mixing ratio by volume of1/13, the target 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propenewas eluted and collected in an amount of 1.15 g in the form of whitecrystals. The resultant target compound was obtained in an isolationyield of 88%.

The physical property data of1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene are shown below.

¹H-NMR (300 MHz, CDCl₃) δ=1.56 (3H, d, J=1.5 Hz), 2.15 (3H, s), 3.18(2H, s), 5.92 (2H, s), 6.63 (1H, dd, J=7.8 Hz, J=1.5 Hz), 6.67 (1H, d,J=1.5 Hz), 6.72 (1H, d, J=7.8 Hz), 7.02 (1H, q, J=1.5 Hz).

¹³C-NMR (75.5 MHz, CDCl₃) δ=13.43, 20.78, 40.05, 100.86, 108.10, 109.10,121.31, 121.70, 131.24, 132.79, 146.08, 147.69, 168.26.

Elemental Analysis

C (%) H (%) Calculated for C₁₃H₁₄O₄ 66.66 6.02 Found 66.71 6.16

Example 2

In an argon gas atmosphere at a temperature of 20° C., a 20 ml flask wascharged with a mixed solution of 6.83 g (55.97 m moles) of1,2-methylenedioxybenzen and 0.96 g (4.88 m moles) of3,3-diacetoxy-2-methylpropene in a purity degree of 88.0% by mass, andthe mixed solution was mixed with 77 mg (0.54 m mole) of borontrifluoride-diethylether complex. The resultant mixture was stirred at atemperature of 23° C. for one hour to provide a reaction liquid. Thereaction liquid was mixed with 100 ml of acetonitrile.

The resultant reaction liquid was subjected to a high performance liquidchromatographic analysis in accordance with an absolute calibrationcurve method. In the result of the analysis, the yield of1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was 97.1%. Also,the reaction liquid contained non-reacted 1,2-methylenedioxybenzene inan amount of 5.86 g.

Examples 3 to 6

In each of Examples 3 to 6, the same reaction and analysis as in Example2 were carried out, except that a 1,2-methylenedioxybenzene,3,3-diacetoxy-2-methylpropene and boron trifluroride-ether complex wereemployed in the amounts as shown in Table 1 and the reaction temperatureand the reaction time were changed as shown in Table 1.

The reaction results are shown in Table 1.

TABLE 1 Reaction Reaction Yield of Compound 1 Compound 2 BF₃.Et₂Otemperature time compound 3 (mmol)⁽*⁾¹ (mmol)⁽*⁾² (mmol)⁽*⁾⁴ (° C.) (h)(%)⁽*⁾³ Example 3 27.99 5.55 0.54 0 2 84.6 4 27.94 5.55 0.56 23 1 89.3 527.94 5.55 0.27 23 3 86.8 6 55.95 5.61 5.58 23 0.5 93.8 Note:⁽*⁾¹Compound 1: 1,2-methylenedioxybenzen ⁽*⁾²Compound 2:3,3-diacetoxy-2-methylpropene ⁽*⁾³Compound 3:1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl) propene ⁽*⁾⁴BF₃ 19 Et₂O:Boron triflate-diethylethel complex

Comparative Example 1

In an-argon gas atmosphere, a 25 ml three necked flask was charged with1.28 g (6.7 m moles) of titanium tetrachloride and then with 0.017 g(0.12 m mole) of boron trifluoride-diethylether complex. In theresultant mixture, 3.27 g (26.8 m moles) of 1,2-methylenedioxybenzenewere added dropwise over a time of 60 minutes at an internal temperatureof the flask of 8 to 12° C. and then a mixture 1.05 g (6.1 m moles) of3,3-diacetoxy-2-methylpropene in a purity degree of 100% by mass with0.75 g (6.1 m moles) of 1,2-methylenedioxybenzene was added dropwiseover 15 minutes. The resultant mixture was stirred at an internaltemperature of 8 to 10° C for 30 minutes, then mixed with 10 ml of a6N-hydrochloric acid and 10 ml of dichloromethane and the resultantmixture was stirred for 30 minutes. From the resultant mixture, theresultant insoluble fraction was separated by filtration, the resultantfiltrate was mixed with dichloromethane to apply an extraction treatmentto the filtrate. The resultant organic layer was separated andcollected, washed with water, further washed with a saturated aqueoussodium chloride solution and then dried on anhydrous sodium sulfate. Theresultant liquid material was subjected to filtration and concentrationtreatments. A crude product was obtained in an amount of 3.16 g. Thecrude product was subjected to a high performance liquid chromatographicanalysis in accordance with the absolute calibration curve method. Inthe analysis results, the yield of the target1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was 43.1% and theresultant reaction liquid contained non-reacted1,2-methylenedioxybenzene in an amount of 1.40 g.

Comparative Example 2

In an argon gas atmosphere, a three necked flask having a capacity of 25ml was charged with 0.10 g (0.5 m moles) of titanium tetrachloride andthen 0.94 g (5.0 m moles) of 3,3-diacetoxy-2-methylpropene in a puritydegree of 91.7% by mass was placed dropwise into the flask at aninternal temperature of 4 to 5° C. To the resultant mixture, 6.11 g(50.0 m moles) of 1,2-methylenedioxybenzene were added dropwise. Thetemperature of the resultant reaction mixture was raised to 23° C., andthe resultant mixture was stirred for 18 hours. The resultant reactionliquid was mixed with 20 g of ethyl alcohol. The resultant liquidmaterial was subjected to a high performation liquid chromatographicanalysis in accordance with the absolute calibration curve method. Inthe analysis results, the yield of the target1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was 9.8%.

Example 7

In an argon gas atmosphere at a temperature of 20° C., a flask having acapacity of 25 ml was charged with a mixed solution of 6.83 g (56.0 mmoles) of 1,2-methylenedioxybenzen with 152 mg (1.12 m moles) of zincchloride. Then, the mixed solution was mixed with 0.96 g (5.60 m moles)of 3,3-diacetoxy-2-methylpropene in a content of 100% by mass. The mixedsolution was stirred at an internal temperature of 23° C. for 3 hours toprovide a reaction liquid. The reaction liquid was mixed with 85 ml ofacetonitrile. The resultant mixed liquid was subjected to a highperformance liquid chromatography to analyze the mixed liquid inaccordance with the absolute calibration curve method. In the analysisresult, the yield of the target1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was 88.3%.

The resultant reaction liquid contained 6.06 g of non-reacted1,2-methylenedioxybenzene.

Example 8

In an argon gas atmosphere at a temperature of 20° C., a flask having acapacity of 25 ml was charged with a mixed solution of 2.44 g (20.0 mmoles) of 1,2-methylenedioxybenzen and a 72 mg (0.20 m mole) of coppertriflate, and the mixed solution was mixed with 0.38 g (2.0 m moles) of3,3-diacetoxy-2-methylpropene in a content of 100% by mass, and themixed solution was stirred at an internal temperature of 22° C. for 6hours. The resultant mixture was mixed with ethanol in an amount of 10ml.

The resultant reaction liquid was subjected to a high performance liquidchromatographic analysis in accordance with the absolute calibrationcurve method. In the analysis results, the yield of1-acetoxy-2-methyl-3-(3, 4-methylenedioxyphenyl)propene was 84%, and thereaction liquid contained 2.17 g of non-reacted1,2-methylenedioxybenzene.

Examples 9 to 11

In each of Examples 9 to 11, the same reaction as in Example 7 wascarried out, with the following exceptions.

The amounts of 1,2-methylenedioxybenzene, 3,3-diacetoxy-2-methylpropeneand zinc chloride and the reaction time were changed to as shown inTable 2. The results are shown in Table 2.

TABLE 2 Zinc Reaction Reaction Yield of Compound 1 Compound 2 Chloridetemperature time compound 3 (mmol)⁽*⁾¹ (mmol)⁽*⁾² (mmol) (° C.) (h)(%)⁽*⁾³ Example  9 55.97 5.95 0.54 23 6 82.1 10 55.88 5.58 2.81 23 190.0 11 27.96 5.62 1.16 23 2 81.9 Note: ⁽*⁾¹Compound 1:1,2-methylenedioxybenzene ⁽*⁾²Compound 2: 3,3-diacetoxy-2-methylpropene⁽*⁾³Compound 3: 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl) propene

Example 12

In an argon gas atmosphere, a four necked flask having a capacity of 200ml was charged with 19.22 g (100 m moles) of3,3-diacetoxy-2-methylpropene having a purity degree of 89.6% by massand 108.14 g (1.0 mole) of anisol. Then, the resultant mixture was mixedwith 1.42 g (10 m moles) of boron trifluoride-diethylether complex at aninternal temperature of 24° C. for 2 minutes. The mixture was stirred atan internal temperature of 24 to 25° C. for one hour to cause the mixedpropene compound and anisol to react with each other. After the reactionwas completed, the resultant reaction liquid was washed two times with20 ml of water and further with 20 ml of saturated aqueous sodiumchloride solution. The resultant reaction liquid was subjected to alayer separation treatment, the resultant organic layer was removed by adistillation under reduced pressure (20 mmHg, 55 to 57° C.), theresultant residue was refined by a chromatography on silica gel using aneluting solvent:hexane/ethyl acetate mixture in a mixing volume ratio:10/1. As a colorless liquid fraction, the target1-acetoxy-2-methyl-3-(4-methoxyphenyl)propene was obtained in a yield of93.4% in an amount of 20.58 g.

Example 13

In an argon gas atmosphere, a three necked flask having a capacity of 25ml was charged with 1.92 g (10 m moles) of 3,3-diacetoxy-2-methylpropenehaving a purity degree of 89.6% by mass and 13.82 g (100 m moles) ofhydroquinone dimethylether. Then, the resultant mixture was mixed with0.14 g (1 m mole) of boron trifluoride-diethyl ether complex at aninternal temperature of 54° C. over a time of one minute. The mixturewas stirred at an internal temperature of 53 to 54° C. for one hour tocause the mixed compounds to react with each other. After the reactionwas completed, the resultant reaction liquid was mixed with 150 ml ofethyl acetate and washed two times with 20 ml of saturated aqueoussodium chloride solution. The resultant reaction liquid was subjected toa layer separation treatment, the resultant organic layer was distilledunder reduced pressure (20 mmHg, 55 to 57° C.), the resultant residuewas refined by a chromatography on silica gel using an elutingsolvent:hexane/ethyl acetate mixture in a mixing ratio by volume of10/1. As a colorless liquid fraction, the target1-acetoxy-2-methyl-3-(2,5-dimethoxyphenyl)propene was obtained in ayield of 77.4% in an amount of 1.94 g in the form of a colorless solid.

The physical property data of 1-acetoxy-2-methyl-3-(2,5-dimethoxyphenyl)propene are shown below.

¹H NMR (300 MHz, CDCl₃) δ:1.63 (3H, d, J=1.5 Hz), 2.13 (3H, s), 3.26(2H, s), 3.75 (3H, s), 3.77 (3H, s), 6.70–6.74 (2H, m), 6.78 (1H, d,J=9.6 Hz), 6.99 (1H, q, J=1.5 Hz).

¹³C NMR (75.5 MHz, CDCl₃) δ:13.75, 20.76, 33.73, 55.66, 56.06, 111.57,120.58, 128.67, 131.58, 151.98, 153.55, 168.17.

HRMS (EI)(M+)

Calculated for C₁₄H₁₈O₄: 250.1205

Found: 250.1198

Example 14

In an argon gas atmosphere, a three necked flask having a capacity of 25ml was charged with 1.92 g (10 m moles) of 3,3-diacetoxy-2-methylpropenehaving a purity degree of 89.6% by mass and 13.82 g (100 m moles) ofhydroquinone dimethylether. Then, the resultant mixture was mixed with0.14 g (1 m mole) of boron trifluoride-ether complex at an internaltemperature of 54° C. for one minute. The mixture was stirred at aninternal temperature of 53 to 54° C. for one hour to cause the mixedcompounds to react with each other. After the reaction was completed,the resultant reaction liquid was subjected to a quantitative analysisusing a high performance liquid chromatography. It was confirmed thatthe target 1-acetoxy-2-methyl-3-(2,5-dimethoxyphenyl)propene wasproduced in an amount of 2.16 g (yield: 86.0%).

Example 15

In an argon gas atmosphere, a four necked flask having a capacity of 100ml was charged with 69.2 g (500 m moles) of 1,2-dimethoxybenzene and9.61 g (50 m moles) of 3,3-diacetoxy-2-methylpropene having a puritydegree of 89.6% by mass. Then, the resultant mixture was mixed with 1.36g (10 m moles) of zinc chloride at an internal temperature of 25 to 26°C. The mixture was stirred at an internal temperature of 25 to 26° C.for 1.5 hours to cause the mixed compounds to react with each other.After the reaction was completed, the resultant reaction liquid waswashed three times with 50 ml of saturated aqueous sodium chloridesolution. The resultant reaction liquid was subjected to a layerseparation treatment, the resultant organic layer was collected andsubjected to a distillation under reduced pressure (8 to 10 mmHg, 80 to84° C.), the resultant residue was refined by a chromatography on silicagel using an elusion solvent:hexane/ethyl acetate mixture in a mixingratio by volume of 10/1. The target1-acetoxy-2-methyl-3-(3,4-dimethoxyphenyl)propene was obtained in ayield of 95.1% in an amount of 11.9 g in the form of a colorless liquid.

Example 16

In an argon gas atmosphere, a three necked flask having a capacity of 25ml was charged with 13.82 g (100 m moles) of 1,2-dimethoxybenzene and1.87 g (10 m moles) of 3,3-diacetoxy-2-methylpropene having a puritydegree of 92.0% by mass. Then, the resultant mixture was mixed with0.142 g (1 m mole) of boron trifluoride-ether complex at an internaltemperature of 18 to 19° C. The mixture was stirred at an internaltemperature of 22 to 23° C. for 2 hours. After the reaction wascompleted, the resultant reaction liquid was subjected to a quantitativeanalysis using a high performance liquid chromatography. In the result,the target 1-acetoxy-2-methyl-3-(3,4-dimethoxyphenyl)propene wasobtained in a yield of 94.4% (amount: 2.36 g).

Comparative Example 3

In an argon gas atmosphere, a three necked flask having a capacity of 25ml was charged with 1.18 g (62 m moles) of titanium tetrachloride andthen with 0.016 g (0.11 m mol) of boron trifluoride ether complex. Intothe mixture, 3.40 g (24.6 m moles) of 1,2-dimethoxybenzene were addeddropwise at an internal temperature of 8 to 12° C. for 30 minutes andthereafter a mixture of 0.96 g (5.6 ml) of 3,3-diacetoxy-2-methylpropenehaving a purity degree of 100% by mass and 0.77 g (5.6 m moles) of1,2-dimethoxybenzene were added dropwise for 5 minutes. The resultantmixture was stirred at an internal temperature of 8 to 10° C. for 60minutes, and then the resultant mixture was mixed with 10 ml of a 6Nhydrochloric acid and 10 ml of dichloromethane, and stirred for 30minutes. The resultant reaction liquid was filtered to remove ainsoluble fraction from the reaction liquid. The filtrate was extractedwith dichloromethane, the resultant organic layer was washed with water,then with a saturated aqueous sodium chloride solution, and dried overNa₂SO₄. The resultant reaction liquid was filtered, the resultantfiltrate was concentrated. A crude product was obtained in an amount of4.54 g. The crude product was subjected to a quantitative analysis usinga high performance liquid chromatography. As a result, it was found thatthe target 1-acetoxy-2-methyl-3-(3,4-dimethoxyphenyl)propene wasobtained in a yield of 12% (amount: 0.18 g).

The resultant product had a brown color and by an analysis using thehigh performance liquid chromatography, a plurality of by-products wereconfirmed to be contained in the product.

Example 17

In an argon gas atmosphere, a three necked flask having a capacity of100 ml was charged with 1.86 g (3 m moles) of ytterbium triflate(ytterbium trifluoromethanesulfonate) and then with 61.38 g (502.6 mmoles) of 1,2-methylenedioxybenzene. The mixed liquid in the flask wasmixed with 19.30 g (100.0 m moles) of 3,3-diacetoxy-2-methylpropenehaving a purity degree of 89.2% by mass at an internal temperature of 38to 40° C. for 30 minutes. The resultant mixed liquid was stirred at aninternal temperature of 40 to 41° C. for 3 hours. The resultant reactionmixed liquid was washed three times with 16 ml of water, and after eachwashing step was completed, the wasted washing water was evaporated todryness to recover ytterbium triflate. Separately, the water-washedorganic fraction of the reaction liquid was subjected to a quantitativeanalysis using a high performance liquid chromatography. It was foundthat the target 1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propenewas obtained in an amount of 19.57 g in an yield of 83.6%.

Example 18

In an argon gas atmosphere, a three necked flask having a capacity of 25ml was charged with 3.44 g (17.8 m moles) of3,3-diacetoxy-2-methylpropene having a purity degree of 89.2% by massand 12.2 g (100.0 mmole) of 1,2-methylenedioxybenzene. Then, theresultant mixture was mixed with 0.23 g (0.6 m mole) of ytterbiumtrichloride hexahydrate at an internal temperature of 39° C. Theresultant reaction mixture was stirred at an internal temperature of 39to 40° C. for 3 hours.

The resultant reaction liquid was diluted with acetonitrile andsubjected to a quantitative analysis using a high performance liquidchromatography. It was found that the target1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was obtained inan amount of 3.89 g in a yield of 93.1%.

Example 19

In an argon gas atmosphere, a three necked flask having a capacity of 25ml was charged with 3.86 g (20.0 m moles) of3,3-diacetoxy-2-methylpropene having a purity degree of 89.2% by massand 12.212 g (100.0 m moles) of 1,2-methylenedioxybenzene. Then, theresultant mixture was mixed with 0.37 g (0.6 m mole) of ytterbiumtriflate (recovered in Example 17) at an internal temperature of 38° C.The mixture was stirred at an internal temperature of 39 to 40° C. for 3hours.

The resultant reaction liquid was diluted with acetonitrile andsubjected to a quantitative analysis using a high performance liquidchromatography. It was found that the target1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was obtained inan amount of 3.64 g in a yield of 77.7%.

Example 20

In an argon gas atmosphere, a three necked flask having a capacity of 25ml was charged with 3.86 g (20.0 m moles) of3,3-diacetoxy-2-methylpropene having a purity degree of 89.2% by massand 12.21 g (100.0 m moles) of 1,2-methylenedioxybenzene. Then, theresultant mixture was mixed with 0.25 g (0.6 m mole) of tin triflate atan internal temperature of 38° C. The mixture was stirred at an internaltemperature of 39 to 40° C. for 3 hours.

The resultant reaction liquid was diluted with acetonitrile andsubjected to a quantitative analysis using a high performance liquidchromatography. It was found that the target1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was obtained inan amount of 4.10 g in a yield of 87.6%.

Example 21

In an argon gas atmosphere, a three necked flask having a capacity of 25ml was charged with 3.86 g (20.0 m moles) of3,3-diacetoxy-2-methylpropene having a purity degree of 89.2% by massand 12.21 g (100.0 m moles) of 1,2-methylenedioxybenzene. Then, theresultant mixture was mixed with 0.16 g (0.6 m mole) of tintetrachloride at an internal temperature of 38° C. The mixture wasstirred at an internal temperature of 39 to 40° C. for 3 hours.

The resultant reaction liquid was diluted with acetonitrile andsubjected to a quantitative analysis using a high performance liquidchromatography. It was found that the target1,-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was obtained inan amount of 4.15 g in a yield of 88.5%.

Example 22

In an argon gas atmosphere, a three necked flask having a capacity of 25ml was charged with 3.86 g (20.0 m moles) of3,3-diacetoxy-2-methylpropene having a purity degree of 89.2% by massand 12.21 g (100.0 m moles) of 1,2-methylenedioxybenzene. Then, theresultant mixture was mixed with 0.36 g (0.6 m mole) of cerium triflateat an internal temperature of 38° C. The mixture was stirred at aninternal temperature of 39 to 40° C. for 3 hours.

The resultant reaction liquid was diluted with acetonitrile andsubjected to a quantitative analysis using a high performance liquidchromatography. It was found that the target1,-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was obtained inan amount of 3.64 g in a yield of 77.7%.

Example 23

In an argon gas atmosphere, a three necked flask having a capacity of 25ml was charged with 3.86 g (20.0 m moles) of3,3-diacetoxy-2-methylpropene having a purity degree of 89.2% by massand 12.21 g (100.0 m moles) of 1,2-methylenedioxybenzene. Then, theresultant mixture was mixed with 0.37 g (0.6 m mole) of dysprosiumtriflate at an internal temperature of 38° C. The mixture was stirred atan internal temperature of 39 to 40° C. for 3 hours.

The resultant reaction liquid was diluted with acetonitrile andsubjected to a quantitative analysis using a high performance liquidchromatography. It was found that the target1,-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was obtained inan amount of 3.26 g in a yield of 69.6%.

Example 24

In an argon gas atmosphere, a three necked flask having a capacity of 25ml was charged with 3.86 g (20.0 m moles) of3,3-diacetoxy-2-methylpropene having a purity degree of 89.2% by massand 12.21 g (100.0 m moles) of 1,2-methylenedioxybenzene. Then, theresultant mixture was mixed with 0.37 g (0.6 m mole) of holmium triflateat an internal temperature of 38° C. The mixture was stirred at aninternal temperature of 39 to 40° C. for 3 hours.

The resultant reaction liquid was diluted with acetonitrile andsubjected to a quantitative analysis using a high performance liquidchromatography. It was found that the target1,-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was obtained inan amount of 3.56 g in a yield of 76.1%.

Example 25

In an argon gas atmosphere, a three necked flask having a capacity of 25ml was charged with 3.86 g (20.0 m moles) of3,3-diacetoxy-2-methylpropene having a purity degree of 89.2% by massand 12.21 g (100.0 m moles) of 1,2-methylenedioxybenzene. Then, theresultant mixture was mixed with 0.37 g (0.6 m mole) of lutetiumtriflate at an internal temperature of 38° C. The mixture was stirred atan internal temperature of 39 to 40° C. for 3 hours.

The resultant reaction liquid was diluted with acetonitrile andsubjected to a quantitative analysis using a high performance liquidchromatography. It was found that the target1,-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was obtained inan amount of 3.91 g in a yield of 83.5%.

Example 26

In an argon gas atmosphere, a three necked flask having a capacity of 25ml was charged with 3.86 g (20.0 m moles) of3,3-diacetoxy-2-methylpropene having a purity degree of 89.2% by massand 12.21 g (100.0 m moles) of 1,2-methylenedioxybenzene. Then, theresultant mixture was mixed with 0.370 g (0.6 m mole) of thuliumtriflate at an internal temperature of 38° C. The mixture was stirred atan internal temperature of 39 to 40° C. for 3 hours.

The resultant reaction liquid was diluted with acetonitrile andsubjected to a quantitative analysis using a high performance liquidchromatography. It was found that the target1,-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was obtained inan amount of 3.89 g in a yield of 82.9%.

Example 27

In an argon gas atmosphere, a three necked flask having a capacity of 25ml was charged with 3.86 g (20.0 m moles) of3,3-diacetoxy-2-methylpropene having a purity degree of 89.2% by massand 12.21 g (100.0 m moles) of 1,2-methylenedioxybenzene. Then, theresultant mixture was mixed with 0.37 g (0.6 m mole) of erbium triflateat an internal temperature of 38° C. The mixture was stirred at aninternal temperature of 39 to 40° C. for 3 hours.

The resultant reaction liquid was diluted with acetonitrile andsubjected to a quantitative analysis using a high performance liquidchromatography. It was found that the target1,-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene was obtained inan amount of 3.77 g in a yield of 80.5%.

Example 28

In an argon gas atmosphere, a three necked flask having a capacity of 25ml was charged with 3.86 g (20.0 m moles) of3,3-diacetoxy-2-methylpropene having a purity degree of 89.2% by massand 10.82 g (100.0 m moles) of anisol. Then, the resultant mixture wasmixed with 0.22 g (0.6 m mole) of copper triflate at an internaltemperature of 38° C. The mixture was stirred at an internal temperatureof 39 to 40° C. for 3 hours.

The resultant reaction liquid was diluted with acetonitrile andsubjected to a quantitative analysis using a high performance liquidchromatography. It was found that the target1,-acetoxy-2-methyl-3-(4-methoxyphenyl)propene was obtained in an amountof 4.09 g in a yield of 92.7%.

Example 29

In an argon gas atmosphere, a three necked flask having a capacity of 25ml was charged with 3.86 g (20.0 m moles) of3,3-diacetoxy-2-methylpropene having a purity degree of 89.2% by massand 11.0 g (101.8 m moles) of anisol. Then, the resultant mixture wasmixed with 0.37 g (0.6 m mole) of ytterbium triflate at an internaltemperature of 38° C. The mixture was stirred at an internal temperatureof 39 to 40° C. for 3 hours.

The resultant reaction liquid was diluted with acetonitrile andsubjected to a quantitative analysis using a high performance liquidchromatography. It was found that the target1,-acetoxy-2-methyl-3-(4-methoxyphenyl)propene was obtained in an amountof 4.15 g in a yield of 94.2%.

Example 30

In an argon gas atmosphere, a three necked flask having a capacity of 25ml was charged with a mixture of 7.04 g (51.7 m moles) of1,2-ethylenedioxybenzene having a purity degree of 97% by mass with 0.97g (5.0 m moles) of 3,3-diacetoxy-2-methylpropene having a purity degreeof 89.2% by mass, and then the mixture was further mixed with 71 mg (0.5m mole) of boron trifluoride-ether complex at an internal temperature of24° C. The mixture was stirred at an internal temperature of 24° C. for2 hours.

The resultant reaction liquid was mixed with 50 ml of ethyl acetate, andthe resultant organic layer was washed twice with 50 ml of water anddried over anhydrous sodium sulfate, and the solvent was removed bydistillation. The distillation residue was subjected to a columnchromatography on silica gel and treated with an eluting solvent: ethylacetate/n-hexane mixture in a mixing ratio by volume of 1/5. The target1-acetoxy-2-methyl-3-(3,4-ethylenedioxyphenyl)propene in an oily statewas obtained in an amount of 0.97 g. The isolation yield of the targetcompound was 78.2%.

The physical property data of 1-acetoxy-2-methyl-3-(3,4-ethylenedioxyphenyl)propene are shown below.

¹H-NMR (300 MHz, CDCl₃) δ:1.59 (3H, d, J=1.5 Hz), 2.14 (3H, s), 3.15(2H, s), 4.23 (4H, s), 6.64 (1H, dd, J=8.1 Hz, J=2.0 HZ), 6.69 (1H, d,J=2.0 Hz), 6.77 (1H, d, J=8.1 Hz), 7.02 (1H, q, J=1.5 Hz).

HRMS (EI)(M+)

Calculated for C₁₄H₁₆O₄: 248.1049.

Found: 248.1051.

INDUSTRIAL APPLICABILITY

The process enables a 1-acetoxy-3-(substituted phenyl)propene compounduseful, as an intermediate, for perfumes, pharmaceutical chemicals,agricultural chemicals and other organic synthetic chemicals, to beeasily produced in a high yield. Thus the process for producing1-acetoxy-3-(substituted phenyl)propene compounds has a highapplicability in industry. Also, the 1-acetoxy-3-(substitutedphenyl)propene compounds produced by the process include new compounds.

1. A process for producing a 1-acetoxy-3-(substituted phenyl) propenecompound represented by the general formula (I):

in which formula (I), R¹ and R², respectively and independently fromeach other, represented a member selected from the groups consisting ofa hydrogen atom and alkyl groups having 1 to 10 carbon atoms, R¹ and R²may form, together with carbon atoms located in the 2- and 3-positionsof the propene group, a cyclic group; and A represents a member selectedfrom a group of substituted phenyl groups represented by the formulae(II) and (III):

wherein R³ and R⁴, respectively and independently from each other,represent an alkyl group having 1 to 4 carbon atoms, m represents aninteger of 0 or 1 to 4, n represents an integer of 1 or 5 and krepresents an integer of 1 or 2, comprising reacting a benzene compoundselected from those represented by the general formulae (IV) and (V):

in which formula (IV) and (V), R³ and R⁴ and n, m and k are as definedabove, with a 2-alkenylidene diacetate compound represented by thegeneral formula (VI):

in which formula (VI), R¹ and R² are as defined above, in the presenceof a catalyst consisting essentially of at least one compound selectedfrom the group consisting of (a) halogenated boron compounds, (b)triflate compounds of Group 11 elements of the Periodic Table, (c)halogenated compounds of Group 12 elements of the Periodic Table, and(d) triflate compounds and halogenated compounds of tin and lanthanoidelements of atomic numbers 58 and 66 to
 71. 2. The process for producinga 1-acetoxy-3-(substituted phenyl)propene compound as claimed in claim1, wherein the benzene compounds represented by the formula (IV) isselected from the group consisting of anisole, veratrol, hydroquinonedimethylether, pyrogallol trimethylether and hydroxyhydroquinonetrimethylether.
 3. The process for producing a 1-acetoxy-3-(substitutedphenyl)propene compound as claimed in claim 1, wherein the benzenecompounds represented by the formula (V) is selected from the groupconsisting of 1,2-methylenedioxybenzene and 1,2-ethylenedioxybenzene. 4.The process for producing a 1-acetoxy-3-(substituted phenyl)propenecompound as claimed in claim 1, wherein the alkenylidene diacetate isselected from the group consisting of 3,3-diacetoxy-1-methylpropene,3,3-diacetoxy propene, 3,3-diacetoxy-1-methylpropene,3,3-diacetoxy-2-ethyl propene, 3,3-diacetoxy-1-ethylpropene, and3,3-diacetoxy-1-ethyl-2-methylpropene.
 5. The process for producing a1-acetoxy-3-(substituted phenyl)propene compound as claimed in claim 1,wherein the reaction is carried out in a molar ratio of the benzenecompound to the alkenylidene diacetate compound of 1:1 to 50:1.
 6. Theprocess for producing a 1-acetoxy-3-(substituted phenyl)propene compoundas claimed in claim 1, wherein the catalyst is present in an amount of0.005 to 1 mole per mole of the alkenylidene diacetate compound.
 7. Theprocess for producing a 1-acetoxy-3-(substituted phenyl)propene compoundas claimed in claim 1, wherein the halogenated boron compounds (a)usable for the catalyst are selected from boron fluorides, borontrifluoride-diethylether complexes, borontrifluoride-tetrahydrofurancomplexes, boron trifluoride-acetic acid complex salt, boron trifluoridedehydrate, and boron trifluoride-n-buthylether complexes.
 8. The processfor producing a 1-acetoxy-3-(substituted phenyl)propene compound asclaimed in claim 1, wherein the triflate compounds (b) of Group 11elements of the Periodic Table usable for the catalyst are selected fromthe group consisting of copper triflate and silver triflate.
 9. Theprocess for producing a 1-acetoxy-3-(substituted phenyl) propenecompound as claimed in claim 1, wherein the halogenated compounds (c) ofGroup 12 elements usable for the catalyst are selected from the groupconsisting of zinc fluoride, zincchloride, zinc bromide, zinc iodide,cadmium fluoride, cadmium chloride, cadmium bromide, cadmium iodide,mercury fluoride, mercury chloride, mercury bromide, and mercury iodide.10. The process for producing a 1-acetoxy-3-(substituted phenyl) propenecompound as claimed in claim 1, wherein the triflate and halogenatedcompounds (d) of tin and lanthanoid elements of atomic numbers 58 and 66to 71 are selected from the group consisting of triflates, fluorides,chloride, bromides, and iodide of tin, cerium, dysprosium, holmium,erbium, thulium, ytterbium and lutetium.
 11. The process for producing a1-acetoxy-3-(substituted phenyl)propene compound as claimed in claim 1,wherein the reaction is carried out in an atmosphere consisting of anonreactive gas to the above-mentioned compounds of the formulae (IV),(V) and (VI), the above-mentioned catalyst and the resultant reactionproducts.
 12. The process for producing a 1-acetoxy-3-(substitutedphenyl)propene compound as claimed in claim 1, wherein the compounds ofthe formula (I) are selected from the compounds represented by thegeneral formula (VII):

in which formula (VII), R¹, R² are as defined above, B represents amember selected from a group of substituted phenyl groups represented bythe formulae (VIII) and (IX):

in which formulae (VIII) and (IX), R³ and R⁴ and k are as defined above.13. The process for producing a 1-acetoxy-3-(substituted phenyl) propenecompound as claimed in claim 1, wherein the compound of the formula (I)is selected from 1-acetoxy-3-(3,4-C1 to C2 alkylene dioxyphenyl)propenesrepresented by the formulae (X) and (XI):

in which formulae (X) and (XI), R¹ and R² are as defined above.
 14. Theprocess for producing a 1-acetoxy-3-(substituted phenyl)propene compoundas claimed in claim 12, wherein in the formulae (X) and (XI), R¹represents a hydrogen atom and R² represents a methyl group.
 15. Theprocess for producing a 1-acetoxy-3-(substituted phenyl)propene compoundas claimed in claim 1, wherein the compound of the formula (I) isselected from the groups consisting of1-acetoxy-2-methyl-3-(3,4-methylenedioxyphenyl)propene,1-acetoxy-2-methyl-3-(3,4-ethylenedioxyphenyl)propene,1-acetoxy-2-methyl-3-(4-methoxyphenyl) propene,1-acetoxy-2-methyl-3-(2,5-dimethoxyphenyl)propene, and1-acetoxy-2-methyl-3-(3, 4-dimethoxy-phenyl)propene.